Liquid crystalline side chain polymer with a poly (Geraniol-co-MMA) backbone and phenylbenzoate mesogenic group: synthesis and characterization

A new side chain liquid crystalline polymers have been synthesized and characterized in which [geraniol-co-MMA] polymer are used as a backbone linked via polymethylene spacer to phenyl benzoate mesogenic group. The polymer exhibits enantiotropic liquid crystallinity with nematic phase and does not exhibit side chain crystallization .A clear difference between the nature of the mesophase is evidenced between [Geraniol-co-MMA] main chain and methacrylate polymers .The LC polymer exhibit glass transition at 40 °C. In a comparative analysis, we discuss the relevance of polymer backbone in the synthesis of side chain liquid crystalline polymers.     

MORPHOLOGICAL STUDIES OF A THERMOTROPIC SIDE-CHAIN LIQUID CRYSTALLINE POLYMER DURING MESOPHASE TRANSITIONS*

The morphological features of a side-chain liquid crystalline polymer during the mesophasetransitions were investigated by using the DSC technique. The polymer used was polyacrylate with mesogensof three benzene rings attached to the main chain through a flexible spacer. A special two-phase texture wasobserved in the transition temperature range. Similar to main-chain liquid crystalline polymers the transitionprocess of the side-chain liquid crystalline polymer was composed of an initiation of the new phase at localplaces of the old phase matrix and a growth process of the new phase domains.     

STUDY OF CHIRAL SIDE CHAIN LIQUID CRYSTALLINE POLYMERS

Five kinds of side chain liquid crystalline polymers with a chiral component in the pendant group were synthesized and characterized by GPC, polarizing microscopy, DSC, X-ray diffraction ano Dielectric Relaxation Spectroscopy. The liquid crystalline behaviour of the polymers is affected by the length of flexible spacer, which links the mesogenic side chain to the polymer backbone and mesogenic moiety. The characteristic of smectic phase is observed for all the polymers.     

Tailoring the liquid crystalline property via controlling the generation of dendronized polymers containing azobenzene mesogen

The first‐ and second‐generation dendronized polymers containing azobenzene mesogen were designed and successfully synthesized via free radical polymerization. The chemical structures of the monomers were confirmed by elemental analysis, ¹H NMR, and ¹³C NMR. The molecular characterizations of the polymers were performed with ¹H NMR and gel permeation chromatography. The phase structures and transition behaviors were studied using differential scanning calorimetry, polarized light microscopy, and small‐angle X‐ray scatter experiments. The experiment results revealed that the first‐generation dendronized polymer exhibited liquid crystalline behavior of the conventional side‐chain liquid crystalline polymer with azobenzene mesogen, that is, the polymer exhibited smectic phase structure at lower temperature and nematic phase structure at higher temperature. However, the second‐generation dendronized polymers exhibited more versatile intriguing liquid crystalline structures, namely smectic phase structure at lower temperature and columnar nematic phase structure at higher temperature, and moreover, the phase structure still remained before the decomposition temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1149–1159, 2010     

新型侧链液晶M5MPP/MMEANB高聚物的合成与表征

以4,4'-二羟基联苯、4-硝基苯胺、二溴己烷、甲基丙烯酸、氯代乙醇为原料合成了单体甲基丙烯酸[5(4'-甲氧基联苯4氧基)戊基]酯(M5MPP)、4-硝基偶氮苯基甲基-2-甲基丙烯酸酯基乙胺(MMEANB),并完成了单体的聚合和共聚,得到了含有非线性光学活性基团(NLO)的侧链液晶高分子,对其结构进行了表征.结果表明,均聚物PM5MPP及共聚物(M5MPP/MMEANB)属双向液晶高分子;PMMEANB属于非晶性高分子.证实了分子间吸电子与给电子基团相互作用有利于提高液晶高分子热稳定性,共聚物(M5MPP/MMEANB)具有较宽的液晶相温度范围.     

Liquid crystalline conjugated polymers and their applications in organic electronics

This article describes the syntheses and electro‐optical applications of liquid crystalline (LC) conjugated polymers, for example, poly(p‐phenylenevinylene), polyfluorene, polythiophene, and other conjugated polymers. The polymerization involves several mechanisms: the Gilch route, Heck coupling, or Knoevenagel condensation for poly(p‐phenylenevinylene)s, the Suzuki‐ or Yamamoto‐coupling reaction for polyfluorenes, and miscellaneous coupling reactions for other conjugated polymers. These LC conjugated polymers are classified into two types: conjugated main chain polymers with long alkyl side chains, namely main‐chain type LC polymers, and conjugated polymers grafting with mesogenic side groups, namely side‐chain type LC conjugated polymers. In general, the former shows higher transition temperature and only nematic phase; the latter possesses lower transition temperature and more mesophases, for example, smectic and nematic phases, depending on the structure of mesogenic side chains. The fully conjugated main chain promises them as good candidates for polarized electroluminescent or field‐effect devices. The polarized emission can be obtained by surface rubbing or thermal annealing in liquid crystalline phase, with maximum dichroic ratio more than 20. In addition, conjugated oligomers with LC properties are also included and discussed in this article. Several oligo‐fluorene derivatives show outstanding polarized emission properties and potential use in LCD backlight application. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2713–2733, 2009     

Thermotropic main chain liquid crystalline polyesters containing ferrocene and phosphate units: synthesis and characterization

A new series of liquid crystalline main chain copolyesters were prepared, having ferrocene in the mesogenic segment and a methyl phosphate group along with a methylene spacer. The even numbered methylene groups were varied from two to ten. Liquid crystalline behaviour was investigated on a hot stage optical polarized microscope. Thermal properties of the polymers were analysed by TGA and DSC, revealing that the polymers yield high char products, probably caused by the formation of phosphorus and iron oxides. The glass transition (T_g) temperatures of the polymers were found to be fairly low, the result of the incorporation of bulky phosphorus and ferrocene moieties in the chain. The phase behaviour was analysed and correlated with the structure of the polymers. The liquid crystalline textures of the polymers became more transparent with increasing spacer length. Energy minimized structures for the polymer repeating units reveal that both the ferrocene and phosphorus moieties produce more molecular entanglement, thus reducing the T_g and T_m of the polymers.     

Electromechanical effects in ferroelectric liquid crystalline polymers

Electric fields can induce mechanical vibrations in planar aligned sandwich cells of ferroelectric liquid crystals. Measurements on a polysiloxane and a polyacrylate side chain polymer proved that the electromechanical effect also exists in ferroelectric liquid crystalline polymers. The main characteristics of the electromechanical responses of these polymers are described and compared to the response of low molecular weight ferroelectric liquid crystals. According to the proposed interpretation, the vibrations in the direction parallel to both the smectic layers and cell substrates are due to coupling between the director rotation and the flow, while the resonances in the vibrations normal to the plates are connected to layer deformations.     

The photophysical properties and morphology of fluorene-alt-benzene based conjugated polymer

A series of fluorene-alt-benzene based conjugated main chain polymers chemically attached with alkyl side chains of different lengths on phenylene rings were designed and synthesized by a palladium catalyzed Suzuki coupling reaction. The UV-vis absorption and fluorescence spectra, thermal stability of spectral property, phase transition behavior and morphology of the synthesized polymers were investigated. With increasing the length of the alkyl side chain, the UV and fluorescence spectra exhibit an obvious blue shift compared with those of the unsubstituted polymer. The alkyl substitution improves the thermal spectral stability of the polymers due to the steric hindrance of the alkyl side chains, thus leading to efficient separation of the main chain backbones. The phase transition behavior is closely related to the length of the alkyl side chains attached on the phenylene rings. The annealed films of the polymers display characteristic nematic liquid crystalline texture. TEM observations indicate that solvent-cast thin deposits of all the polymers show typical fibrillar morphology.     

液晶性树状高分子

对树状高分子进行功能化,使之成为具有特定性能的新型材料是目前很热门的课题,树状液晶就是其中之一.树状高分子长径比很小,似乎难以形成液晶态,但人们已发现多种树状液晶分子,几乎囊括了所有在其他高分子中出现过的液晶相.本文按液晶相分类,介绍树状液晶高分子的研究进展.     

Thermotropic laterally attached liquid crystalline polymers: I. New stationary phases for high-performance liquid chromatography

Up to now thermotropic liquid crystalline side chain polymers have been seldom used as stationary phases in high-performance liquid chromatography (HPLC). The preparation of a new class of surface modified silica gels is reported. They are obtained by coating on the silica support liquid crystalline polysiloxanes with mesogenic side groups laterally attached to the polymer backbone through a flexible spacer. Their chromatographic behavior in reversed-phase HPLC is described for the separation of polycyclic aromatic hydrocarbons. The results show excellent planarity and rod shape recognition capabilities. Comparisons with low-molecular-mass liquid crystalline-bonded silica and longitudinally attached liquid crystalline polymer-coated stationary phase are also reported. Finally, comparisons to commercially available C₁₈ phases are described for the separation of complex mixtures.     

甲壳型液晶高分子研究进展与展望

简要介绍了甲壳型液晶高分子的模型理论, 概述了当前国内外对甲壳型液晶高分子设计、 液晶相态、 性质及基于甲壳型液晶高分子的嵌段共聚物体系的设计和自组装性质等研究进展, 展望了今后的研究方向.     

Design,synthesis, and characterization of a combined main‐chain/side‐chain liquid crystalline polymer based on mesogen‐jacketed liquid crystal polymer via atom transfer radical polymerization

A novel combined main‐chain/side‐chain liquid crystalline polymer based on mesogen‐jacketed liquid crystal polymers (MJLCPs) containing two biphenyls per mesogenic core of MJLCPs main chain, poly(2,5‐bis{[6‐(4‐butoxy‐4′‐oxy‐biphenyl)hexyl]oxycarbonyl}styrene) (P1–P8) was successfully synthesized via atom transfer radical polymerization (ATRP). The chemical structure of the monomer was confirmed by elemental analysis, ¹H NMR, and ¹³C NMR. The molecular characterizations of the polymer with different molecular weights (P1–P8) were performed with ¹H NMR, gel permeation chromatography (GPC), and thermogravimetric analysis (TGA). Their phase transitions and liquid‐crystalline behaviors of the polymers were investigated by differential scanning calorimetry (DSC) and polarized optical microscope (POM). We found that the polymers P1–P8 exhibited similar behavior with three different liquid crystalline phases upon heating to or cooling in addition to isotropic state, which should be related to the complex liquid crystal property of the side‐chain and the main‐chain. Moreover, the transition temperatures of liquid crystalline phases of P1–P8 are found to be dependent on the molecular weight. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7310–7320, 2008     

聚丙烯酸酯型高分子侧链液晶的合成及其对聚乙烯成核结晶行为的影响

基于聚烯烃用成核剂的结构特征设计合成了两种极性基团和非极性基团交替排列的乙烯基单体,并利用自由基引发聚合,制备出相应的侧链型液晶聚合物.采用元素分析、红外光谱和核磁共振氢谱对所合成单体和聚合物的结构进行了确认.并采用热失重(TGA)和差示扫描量热仪(DSC)研究了聚合物的热稳定性和相转变温度.结果表明,所合成聚合物的起始热分解温度均在337℃以上,具有优异的热稳定性;液晶相变温度区间可达186 K,具有较宽的液晶态温度范围.热台偏光显微镜(HS-POM)研究结果表明,聚合物均呈现出纹影织构,证明所合成的聚合物均为热致向列型侧链液晶高分子.采用DSC和HS-POM研究了所合成的侧链液晶聚合物对高密度聚乙烯(HDPE)异相成核结晶行为的影响.结果表明,侧链型液晶聚合物在提高HDPE结晶温度、结晶度以及降低HDPE晶粒的尺寸及分布方面均有优异的效果,是一类HDPE有效的成核剂.     

Thermotropic main chain liquid crystalline polyesters containing ferrocene and phosphate units: synthesis and characterization

A new series of liquid crystalline main chain copolyesters were prepared, having ferrocene in the mesogenic segment and a methyl phosphate group along with a methylene spacer. The even numbered methylene groups were varied from two to ten. Liquid crystalline behaviour was investigated on a hot stage optical polarized microscope. Thermal properties of the polymers were analysed by TGA and DSC, revealing that the polymers yield high char products, probably caused by the formation of phosphorus and iron oxides. The glass transition (T _g) temperatures of the polymers were found to be fairly low, the result of the incorporation of bulky phosphorus and ferrocene moieties in the chain. The phase behaviour was analysed and correlated with the structure of the polymers. The liquid crystalline textures of the polymers became more transparent with increasing spacer length. Energy minimized structures for the polymer repeating units reveal that both the ferrocene and phosphorus moieties produce more molecular entanglement, thus reducing the T _g and T _m of the polymers.     

Synthesis and properties of mesogen‐jacketed liquid crystalline polymers containing biphenyl mesogen with asymmetric substitutions

This work focuses on the design, synthesis, and characterization of a series of mesogen‐jacketed liquid crystalline polymers (MJLCPs), poly(alkyl 4′‐(octyloxy)‐2‐vinylbiphenyl‐4‐carboxylate) (pVBP(m,8), m = 1, 2, 4, 6, 8, 10, 12). For the first time, we realized asymmetric substitutions in the mesogens of MJLCPs. The polymers obtained by conventional free radical polymerization were investigated in detail by a combination of various techniques, such as differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized light microscopy. Our results showed that all the polymers were thermally stable, and their glass transition temperatures decreased when m increased. The liquid crystalline (LC) phases that developed at high temperatures and disappeared at low temperatures were strongly dependent on the difference in lengths of alkyl groups on the 4 and 4′ substitution positions of the side‐chain biphenyl. While polymer pVBP(1,8) was not liquid crystalline, columnar liquid crystalline phases were observed for all other pVBP(m,8) (m = 2, 4, 6, 8, 10, 12) polymers. Polymer pVBP(8,8) showed a tetragonal columnar nematic liquid crystalline phase, and the other LC polymers exhibited columnar nematic phases. In additions, the smaller the difference in the lengths of the terminal alkyls, the easier the development of the liquid crystalline phase. Birefringence measurements showed that solution‐cast polymer films exhibited moderately high positive birefringence values, indicating potential applications as optical compensation films for liquid crystal displays. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

手性化合物环境下制备甲壳型液晶高分子

甲壳型液晶高分子的研究是我国独创[1 ,2 ] ,已产生了积极的科学影响 .虽然它们在化学结构上属于侧链型 ,但在分子形态上更接近于主链型液晶高分子[3] .由于庞大的液晶基元对空间的要求 ,液晶高分子主链被迫采取尽可能伸展的构象[4,5] .然而 ,至今尚不清楚主链与液晶基元之间是怎样协同作用以形成有序结构 .本文探索了在不同手性化合物环境下制备单手螺旋链甲壳型液晶高分子的可能性 .尽管最后并未获得螺旋链高分子 ,但仍取得了一些有价值的结果 .手性化合物环境分别是 ( )薄荷醇 ( 1 )作为反应溶剂、( )过氧化 二 (碳酸薄荷醇酯 ( 2 )作…     

Liquid crystalline homopolyesters having main chain calamitic mesogens and one or two side chain azobenzene moieties in the repeat units

Combined semi-rigid homopolyesters, containing both main chain calamitic mesogens and one or two side chain azobenzene units separated by aliphatic (hexamethylene, octamethylene and decamethylene) chains in the polymer repeat units, were prepared and their liquid crystalline properties characterized. Polyesters having two side chain azobenzene units and a main chain biphenyl moiety showed a higher ordered smectic B or smectic F phase, whereas the other polymers containing a main chain 2,5-diphenyl-1,3,4-thiadiazole unit and one or two side chain methoxyazobenzene units formed a smectic C phase despite the presence of different mesogens in the main and side chains. This is probably due to the compact molecular chain-packing and intra- and intermolecular interactions between the polymer backbones and the two azobenzene units.     

液晶金属配位聚合物的合成及性能

基于国内外最新研究文献 ,系统论述了近年来液晶金属配位聚合物的合成方法、液晶行为及应用前景。指出液晶金属配位聚合物的合成方法可归纳为直接配位法、单体配位法、交联配位法和聚合物反应法四种。液晶金属配位聚合物一般呈现热致液晶行为 ,显示稳定的向列液晶相或近晶液晶相。有些金属配位聚合物还呈现互变性近晶态或单变液晶性。液晶金属配位聚合物具有金属的特殊性质 ,是一种新型高性能磁导、电导和光导材料 ,可望应用于液晶显示材料、磁性信息储存薄膜材料、润滑剂和各向异性催化剂等。     

Luminescent Iridium-containing liquid crystalline polymers in the side chain

Luminescent liquid crystalline polymers consisting of Iridium attached to polysiloxanes are prepared. 4-Cyanophenyl 4-(allyloxy) benzoate (M₁) and an Iridium complex (Ir-M₂) grafted to poly(methylhydrogeno)siloxane are used for the preparation of the Iridium-containing liquid crystalline polymers. The chemical structures are characterised by Fourier transform infrared spectroscopy and ¹H NMR. The mesomorphic properties and phase behaviour are investigated by differential scanning calorimetry, thermogravimetric analysis, polarising optical microscopy and X-ray diffraction. The polymers containing <1.2 mol% of the Iridium ions reveal reversible mesomorphic phase transition, wide mesophase temperature ranges and high thermal stability. The introduction of the Iridium ions does not change the liquid crystalline state of polymer systems; on the contrary, the polymers are enabled with the luminescent properties. With the Iridium ion contents ranging between 0.3 and 1.2 mol%, luminescent intensity of polymers gradually increased. The temperature dependence of luminescent intensity was studied in the liquid crystalline phase.